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Characterization of nanofiltration membrane

using microscopic methods

ABSTRACT
Surface properties of two nanofiltration membranes NF11 and NF12 were
investigated using Atomic Force Microscope (AFM) and Scanning Electron
Microscope (SEM) in conjunction with two image processing softwares (WSxM 5.0
Develop 6.4 and Image J) in order to predict the one which will give better
performance in the treatment of waste water. Atomic Force Microscope Atomic
Force Microscope of the unused membranes was used in conjunction with
conjunction with WSxM 5.0 Develop 6.4 to study different surface roughness
measures (Bearing ratio,

Power Spectrum Density and Histogram).

The

membranes were scanned on two scan sizes (1.0 m1.0 m and 5.0 m5.0
m). Scanning Electron Microscope (SEM) in conjunction with Image J will be used
to estimate the pore size of both the fresh and used membrane sample as we
progress with the work.
These analyses will help to better understand fouling of nanofiltration
membranes which is a major problem in waste water treatment. The result
showed that NF11 membrane had highest RMS roughness than NF12. The RMS
roughness for 5.0 m5.0 m ranged between 846.263 (NF11) and 691.314
(NF12), whereas for the 1.0 m1.0 m scan size, they ranged between 275.804
(NF11) and 242.406 (NF12). It was concluded that NF11 membrane will give
better performance than NF12 in terms of flux ,there for the analysis that follow
will be done using SEM on unused material and material used to treat waste
water.

TABLE OF CONTENTS
1.

INTRODUCTION.............................................................................................................1

2.

EXPERIMENTAL ANALYSIS.........................................................................................3
2.1. Experimental Set-up............................................................................................3
2.2. Experimental Procedure.....................................................................................4
2.2.1. Atomic Force Microscope (AMF)..............................................................4

3.

RESULTS AND DISCUSSION......................................................................................6


3.1. Bearing Analysis of unused membranes for 1.0 m 1.0 m scan size....................8
3.2. Bearing Analysis of unused membranes for 5.0 m 5.0 m scan size....................9
3.2 Power Spectrum Density Analysis (PSD) for scan size 1.0 m 1.0 m and 5.0 m
5.0 ..................................................................................................................................10

CONCLUSION...............................................................................................................14

REFERENCES.................................................................................................................14

ii

LIST OF FIGURES
Figure 1: Experimental set up.

Figure 2: Bearing ratio plot curve for NF11 and NF12 at 1.0 m 1.0 m. 9
Figure 3: Bearing ratio plot curve for NF11 and NF12 at 5.0m 5.0m. 10
Figure 4: Power spectral density curve for NF11 and NF12 at 1.0m 1.0m.

11

Figure 5: Power spectral density curve for NF11 and NF12 at 5.0m 5.0m.

12

Figure 6: Evolution of the roughness obtained by AFM for 1.0m1.0m and 5.0m5.0m
windows. 13

iii

LIST OF TABLES
Table 1: 2D and 3D images of the membrane surface obtaining by Image
processing software (WSxM 5.0 Develop 6.4).
7
Table 2: Summary of the statistical parameters that were used to quantitatively describe the
surface roughness of the neat membranes with the aid of WXSM 5.0 software
13

iv

1.

INTRODUCTION

Atomic force microscopy is a probe scanning technique commonly used to image


surfaces for producing three-dimensional images; however, an important advantage
of atomic force microscopy in the study of surface properties of materials, including
membrane, is the ability to quantify both surface morphology and surface
interactions with a single instrument [1]. Atomic force microscopy was first used in
1988 to study the structure of polymeric membranes [2]. Atomic force microscopy
can be used under three modes: contact, non-contact and tapping [3]. In contact
mode, the tip is "dragged" across the surface of the sample and the contours of the
surface are measured either using the deflection of the cantilever directly or, more
commonly, using the feedback signal required to keep the cantilever at a constant
position. Thus, contact mode AFM is almost always done at a depth where the
overall force is repulsive, that is, in firm "contact" with the solid surface below any
adsorbed layers [4].
In non-contact mode the tip of the cantilever does not contact the sample surface.
The cantilever is instead oscillated at either its resonant frequency (frequency
modulation) or just above (amplitude modulation) where the amplitude of oscillation
is typically a few nanometers (<10 nm) down to a few picometers. In tapping mode,
the cantilever is driven to oscillate up and down at near its resonance frequency by
a small piezoelectric element mounted in the AFM tip holder similar to non-contact
mode [5]. However, the amplitude of this oscillation is greater than 10 nm, typically
100 to 200 nm. This technique makes it possible to represent no conducting
surfaces with a resolution of the order of the nanometer in either dry or wet
environments [6]. Therefore, using AFM makes it possible to avoid drying the
sample under vacuum. The AFM measurements give access to the roughness, pore
size, pore density and pore size distribution of a membrane [7]. They can also
provide information on the surface electrical properties of a membrane, its fouling
potential towards a specific colloid [8] and its filtration performance as a function of
its roughness.
All this can help to predict fouling without process measurements [9]. Hirose et al.
and Warczock et al. [10] studied the relationship between the skin layer surface
structure of NF membranes and their filtration performances using AFM. It was
1

shown that the roughest membranes provided the best performances in terms of
flux, the flux increases quasi-linearly with the roughness. However, some drawbacks
of the AFM technique were pointed to the following (1) Due to the size of AFM
scanning probe tips, there are some limitations to the scanning depth; also, AFM
may distort membrane pore size due to rounded corners near pore entrance [11].
Boussu et al. [12] compared the results obtained using contact and non-contact
mode AFM. It was concluded that when comparing surface roughness for different
membranes, the same AFM method and the same scan size must be used. However
in this work, non-contact mode was used to analyze surface properties of the two
membranes. In non-contact mode, the tip of the cantilever does not contact the
surface of the sample therefore the sample does not surfer from sample
degradation effects compared to the other modes. In terms of analyzing wet
samples, non-contact mode will be more advantageous since it will just oscillate
above the adsorbed fluid layer to image both the liquid and surface [13].
The main objectives for this analysis is to compare the surface properties of two
nanaofiltration membranes (NF11 and NF12) and to investigate the influence of
membrane factor on fouling relationship of the membranes used to treat waste
water (sewage water). Scanning Electron Microscope (SEM) and Atomic Force
Microscope (AFM) in-conjunction with image processing softwares (WSxM 5.0
Develop 6.4 and Image J) will be used to obtain the following surface parameter of
the membranes, pore size distribution and surface roughness parameters (RMS
roughness, peak height, skewness and kurtosis). Hwang and Lin [14] used
observations made using SEM to qualify the nature of the pores of 3 microfiltration
membranes used to treat waster with a cut-off of 0.1m. They also observed the
fouling of these membranes after filtration of a solution containing model particles
of polymethyl methacrylate (mean diameter = 0.4 m). The major disadvantage of
this technique is the sample preparation by gold metallization, which entails a less
accurate pore size determination [15].
Images obtained by AFM were further analyzed using image processing software
(WSxM 5.0 Develop 6.4) to obtain the statistical measures (bearing ratio, Power
Spectrum Density). The results in the literature shows that the membrane with the
highest roughness will perform better in waste water treatment.
2

2.

EXPERIMENTAL ANALYSIS

Analyses of two different unused nanofiltration membrane materials NF11 and NF12
were performed using Atomic Force Microscope (AFM). The membranes were
scanned on two scan sizes (1.0 m 1.0 m and 5 m 5 m). The four
topographic images obtained from the microscope were stored in a computer and
further analyses using the image processing software WSxM 5.0 Develop 6.4 (see
Figure 1 below).

2.1.

Experimental Set-up

Figure 1: Experimental set up.


3

2.2.

Experimental Procedure

2.2.1. Atomic Force Microscope (AMF)


Atomic force Microscope operated under ambient conditions was used to analyze
the surface roughness of two unused nanofiltration membrane materials. Clean
membranes were cut into small pieces and glued onto a sample holder with an agar
tape before non-contact atomic force microscopy imaging was performed using an
Agilent Technologies 5500 scanning probe microscope (PicoPlus-Atomic Force
Microscopy

Series

5500).

The

AFM

cantilever

used

was

made

of

silicon

(Nanosensors) with a resonant frequency of ~60 kHz, a nominal spring constant of


7.4 N/m with a typical tip radius of less than 7 nm. The atomic force microscopy
measurements were performed on dry membranes in an air atmosphere with
relative humidity of ~30%. The AFM images were flattened with order 1 and the rms
(root

mean-squared)

value

of

the

roughness

was

obtained

by

using

the

Nanotechnology Research Tool [16]. The roughness depends on the scan size;
thereby for the comparative analysis it is required that roughness is obtained from
images with the same scan areas [17]. The atomic force microscopy images of NF11
and NF12 membranes used in the roughness analysis test were done for two
different scan areas. The membrane surface roughness was determined with the
atomic force microscopy and was further analyzed with WXSM 5.0 Develop 6.4
software for bearing ratio analysis. Several statistical parameters like peak height,
skewness, kurtosis, bearing ratio and power spectrum density (PSD) were used to
quantitatively describe the surface roughness of the membranes.
2.2.2 AFM Characterization
The growth of scanning probe microscopy has been parallel to the revolution of
computer technologies. According to Horcas et al [16] stated by Agboola et al [18],
computers have played a central role in the development of this technique
significantly by improving the data acquisition, control, image processing, and data
analysis. WSXM 5.0 software was introduced as a program that can be widely used
by the scanning probe microscopy community. Membrane roughness parameters
were extracted from non-contact mode atomic force microscopy topography image
using instruments software (WXSM 5.0 software) in conjunction with scanning
4

probe microscopy [16]. Phase imaging is an extension of non-contact mode atomic


force microscopy. It was used to enhance the contrast for the features of interest,
providing additional information to the topographical projections [19].

2.2.3 Scanning Probe Microscopy Image Process Roughness Analysis


Surfaces of the nanofiltration membranes were compared in terms of roughness
parameters, such as root mean square rms (nm), the mean roughness ra (nm),
surface skewness (S), and surface kurtosis (K). The roughness parameters depend
on the curvature and the size of the atomic force microscopy tip and the treatment
of the captured surface data (plane fitting, flattering, filtering, etc.). The root mean
square (rms) roughness parameter is a statistical measure of the relative roughness
of a surface and is essentially the standard deviation of the heights for all the pixels
in the image from the arithmetic mean. The root mean square of the roughness
varies with the interval range; it is given by the following expression [16]:

(1)
Where aij is the height value for a particular point on the image (nm),

is the

average/mean height of all the pixels in the image (nm) and N is the total number of
pixels within the image. The maximum range is the height difference between the
lowest and highest pixels in the image.

(2)
The average height

is the mean height of the pixel in the image. It is given by

the following expression:

(3)
The surface skewness (R sk) is the measure of the direction of the asymmetry of the
distribution of heights in the sample:
5

(4)
Where:

(5)
The surface kurtosis (RKU) is the measure of the degree of peaked-ness in the
distribution of heights in the membranes comparing it to the normal distribution.
This statistical parameter is given by the expression in Eq. (5).

(6)
2.3.4 Bearing Analysis
The bearing analysis was used to work out the height information regarding this
study. The term bearing refers to the relative roughness of the sample surface
regarding the high and low area. In bearing analysis, the depths of all pixels of the
image with a particular reference point, e.g., the highest pixel, are analyzed. For
clean membranes, bearing analysis will be used to determine the roughness with
regards to the height distribution. For fouled membranes, bearing analysis will gives
quantitative information about what fraction of the deposited metals are located
above or below a specific bearing plane.
2.3.5 Scanning Electron Microscope (SEM)
Scanning Electron Microscope (SEM) analysis is still to be performed and the images
from this technique will be processed using the image J software to determine the
pore size of both the unused and used membranes.
3.

RESULTS AND DISCUSSION

3.1 Surface Roughness Analysis

Atomic Force Microscope (AFM) was used to obtain information of the topography of
two unused nanofiltration membranes to determine their roughness measures. Four
topographic images at the following scan size (1.0 m 1.0 m and 5.0 m 5.0
m) were taken for each membrane. The surface roughness is an important
structural property of nanofiltration membranes [20]. It has been shown that it can
be related to colloidal fouling [21, 22]. Table 1 shows the noncontact mode images
obtained from AFM for 1.0 m 1.0 m and 5.0 m 5.0 m using the neat NF11
and NF12 together with their corresponding 3D topography images of the same
membrane areas. The topography images represent the membrane top views with
the information on the depth of the membranes in the Z-direction coded in color
intensity with the light regions having the highest points represent the peaks and
the dark region represents the pores. The images of NF11 show a topography
feature with fine network like fibrous structure and the three-dimensional
orthographic images show the occurrence of the peaks and the valleys. An average
roughness of a membrane is defined as an average deviation of peaks and valleys
from the mean plane.

The average of all height obtained by atomic force

microscopy in Table 1 further shows the noncontact mode images of NF12 obtained
from atomic force microscopy for 1.0 m 1.0 m and 5.0 m 5.0 m and their
corresponding three-dimensional topography images of the same membrane areas.
The images have different topography feature from NF11. NF12 have a thick
structure and higher ridges of three-dimensional orthographic. These ridges could
be due to manufacturing artefacts and could be useful landmarks when
investigating the fouled NF12. If the original patterns (ridges) are seen in the fouled
cases, then it can be summarized that there was very little deposition on the
membrane surface. In comparison, NF11 was rougher than NF12 for both scan
areas. According to Bowen et al [23] the higher roughness leads to greater adhesive
strength of the membrane and greater efficiency in the separation process.
Table 1: 2D and 3D images of the membrane surface obtaining by Image processing
software (WSxM 5.0 Develop 6.4).
NF membranes and scan size

45 View

Top view

3.2 Bearing Analysis of unused membranes for 1.0 m 1.0 m scan size

Figure 2 present the comparison of the bearing ratio of NF 11 and NF12 at the same
scan size 1.0 m 1.0 m. Due to the effect of image size on various roughness
parameters, surface roughnesses were compared for identical scan sizes (1.0 m x
1.0 m) scan areas. The height distribution of NF11 was higher than NF12 because
the higher roughness parameters of the unused NF11 leads to greater adhesive
strength of the NF11 and greater efficiency in the separation process of waste
water. The height distributions were centered on a peak for each membrane. The
high peak in NF11 was at 4157.68 nm and the high peak in NF12 was at 3273.32
nm. NF11 distributions have long tails above the peak as a result of wide
distribution of smaller peaks. This shows that NF11 was rougher than NF12.

Figure 2: Bearing ratio plot curve for NF11 and NF12 at 1.0 m 1.0 m.

3.1.

Bearing Analysis of unused membranes for 5.0 m 5.0 m scan size

Figure 3 present the comparison of the bearing ratio analysis of NF11 and NF12 at
the same scan size 5.0m 5.0m. The various roughness parameters, surface
roughnesses were compared for identical scan sizes (5.0 m x 5.0 m) scan areas.
Once again, the height distribution of NF11 was higher than NF12 because the
higher roughness parameters than NF11. This leads to greater adhesive strength of
the NF11 and greater efficiency in the separation process of waste water. The high
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peak in NF11 was at 1215.44 nm and the high peak in NF12 was at 866.036 nm.
NF11 membrane depicted the greatest peak height compared to NF12.

Figure 3: Bearing ratio plot curve for NF11 and NF12 at 5.0m 5.0m.

3.2 Power Spectrum Density Analysis (PSD) for scan size 1.0 m 1.0 m and 5.0 m 5.0

A complete description of nanofiltration membranes surfaces can also be given by


calculating the surface topography using the Power Spectral Density (PSD). This
analysis performs a decomposition of the surface profile into its related spatial
wavelengths and allows comparison of the roughness measurements over different
spatial frequency ranges. The evolution of the membrane morphology was probed
by two-dimensional power spectral density analysis. PSD function provides a
representation of the amplitude of a surface's roughness as a function of the spatial
frequency.
Figure 4 present the PSD plot for NF11 and NF12 obtained from 2D profile for 1.0 m
1.0 m scan size using WSxM 5.0 Develop 6.4 software. The peak for NF11 at 1.0
m 1.0 m scan size is higher than for NF12 and this suggest that NF11 has high
10

surface roughness than NF12. At a selected spatial frequency of 0.0025deg/m, the


peak for NF11 is more shifted to higher spatial frequency compared to NF11. This
also shows that the surface of NF11 is more rough compare to NF12.

Figure 4: Power spectral density curve for NF11 and NF12 at 1.0m 1.0m.

Figure 5 below present the PSD plots for 5.0 m 5.0 m scan size. The peak for
NF11 is also higher than for NF12 at 5.0 m 5.0 m scan size. At a selected
spatial frequency of 0.0005deg/m, the peak for NF11 is more shifted to higher
spatial frequency compared to NF11. This shows that NF11 is more rough compare
to NF12.

11

Figure 5: Power spectral density curve for NF11 and NF12 at 5.0m 5.0m.

Figure 6 below shows RMS roughness of the two membranes at the associated scan
size. It can be seen that whatever the membrane, the RMS roughness obtained for
the 1.0 m 1.0 m is higher than for 5.0 m 5.0 m scan size. The RMS
roughness for 1.0 m 1.0 m ranged between 846.263(NF11) and 691.314
(NF12), whereas for the 5.0 m 5.0 m scan size, the range between 275.804
(NF11) and 242.406 (NF12). In both scan size, the NF11 membrane had the highest
RMS roughness.

12

Figure 6: Evolution of the roughness obtained by AFM for 1.0m1.0m and 5.0m5.0m
windows.

Table: 2 below summarize the roughness measures obtained from the roughness
histogram plot in Figure 2 and Figure 3. The peak height (R p) for 1.0 m 1.0 m
scan size is also higher than that for 5.0 m 5.0 m scan size in both membranes.
However the Skewness (R sk) of NF11 for 1.0 m 1.0 m (0.1267) was higher than
that of 5.0 m 5.0 m (0.031) while the Skewness (R sk) of NF12 was positive for
1.0 m 1.0 m (0.368) and negative for 5.0m 5.0m (-0.0459). This shows
that the surface of NF11 at 1.0 m 1.0 m scan size has deep valleys or high
peaks compared to 5.0 m 5.0 m scan size and lack of peaks on the surface of
NF12. The Kurtosis (Rku) was higher for 1.0 m 1.0 m and less for 5.0 m 5.0
m scan size.

13

Table 2: Summary of the statistical parameters that were used to quantitatively describe the
surface roughness of the neat membranes with the aid of WXSM 5.0 software

4 CONCLUSION
The results obtained shows that the determination of the membrane roughness
depends on the observation scale. The roughness parameters of the membranes
decrease with increase in observation scale. The RMS roughness, peak height,
skewness and kurtosis for 1.0 m 1.0 m scan size were higher than 5.0 m 5.0
m scan size. NF11 membrane had the highest RMS roughness (846.263 nm),
highest peak height (4157.68 nm), highest skewness (0.1267) and kurtosis (3.75) at
1.0 m 1.0 m scan size while NF than NF12 had the lowest (refer in Table 2). The
results clearly show that NF11 was rougher than NF12 since it had the highest
roughness even for 5.0 m 5.0 m scan size. According to Bowen et al [23] the
higher roughness leads to greater adhesive strength of the membrane and greater
efficiency in the separation process. Therefore NF11 will perform better in waste
water treatment.

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